CN101649126A - Recycled thermoplastic composition comprising waste thermoset material and methods of making - Google Patents

Recycled thermoplastic composition comprising waste thermoset material and methods of making Download PDF

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CN101649126A
CN101649126A CN200910166992A CN200910166992A CN101649126A CN 101649126 A CN101649126 A CN 101649126A CN 200910166992 A CN200910166992 A CN 200910166992A CN 200910166992 A CN200910166992 A CN 200910166992A CN 101649126 A CN101649126 A CN 101649126A
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waste
weight
boiled water
plain boiled
particle diameter
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CN101649126B (en
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W·劳
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Rohm and Haas Co
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Rohm and Haas Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/16—Powdering or granulating by coagulating dispersions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C08L19/003—Precrosslinked rubber; Scrap rubber; Used vulcanised rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/30—Polymeric waste or recycled polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2319/00—Characterised by the use of rubbers not provided for in groups C08J2307/00 - C08J2317/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24364—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.] with transparent or protective coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y10T428/2438—Coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y10T428/24405—Polymer or resin [e.g., natural or synthetic rubber, etc.]

Abstract

The present invention provides methods for making shapeable composite materials or shaped articles from recycled materials comprising forming a crumb slurry by, in any order, increasing the particle size of a composition comprising white water waste from one or more emulsion or dispersion polymer and combining the white water waste polymer with one or more waste thermoset material, preferably, ground tire rubber (GTR), and, then processing the combined material wet or dry as a thermoplastic to form the composite material or article. Additionally, shaped articles and composite materials can bemade from substantially all recycled waste materials, such as white water waste from acrylic or vinyl polymer emulsions and waste rubber vulcanizates. The composite materials can consist essentially of reshapeable materials, i.e. without crosslinking agents, thermosettable compositions or compatibilizers to provide reshapeable or recyclable articles.

Description

The thermoplastic compounds and the preparation method that comprise the recovery of waste thermoset material
Technical field
But the present invention relates to substantially all is recovery waste materials manufacturing formed composite material and the method for molded article and the material for preparing by this method that is obtained by plain boiled water polymkeric substance and waste thermoset material.More particularly, it relates to the plain boiled water of the dispersion that comprises condense (coagulated) or emulsion polymer and waste thermoset material for example mouldable (moldable) or the shapable matrix material of vulcanized rubber or vulcanizate, and by the hot formed goods of this Composite Preparation.
Background technology
In the commercial production of emulsion and dispersed polymeres, in the process of batch production end cleaning or flushing reaction vessel, generate many materials; These materials are abandoned as refuse.The product of flushing is also referred to as " plain boiled water ", comprise with commercial polymer in used identical polymkeric substance, but its median size (50-350nm) is too low so that can not concentrate by centrifugation or other known working method.The concentration of flushing product is also far below commercial polymer, and for example, the total polymer solids concn is 0.1 to 2 weight %.Owing to there is not cost-effective mode to use the polymkeric substance of low solid content in the plain boiled water, thereby plain boiled water falls as refuse is processed.
In waste treatment, usually the plain boiled water polymer coagulation is generated slurry, then with slurry and other by product for example mud (biosolid) or mud (sludge) mix, and dewater.The material that obtains is disposed at landfill yard, even it may contain 30 weight % solid polymkeric substance.Except refuse itself, use present treatment process also to comprise a large amount of costs, comprise the cost of 30% solid mud that is processed into ton, refuse is put into the cost of available landfill yard and prepare the cost of weight polymers such as new.
Even the quantity of the plain boiled water that generates in the emulsion polymer in preparation is for 1 weight % of the amount of polymer of preparation or still less, but the total amount that generates is huge, have every year grand total with the waste of polymeric of hundred kilograms by landfill.Therefore, press for the method that effectively to utilize the waste liquid that from the manufacturing of emulsion or dispersed polymeres, produces.
The U.S. patent No.5824673 that authorizes Khait discloses the method for preparing polymer beads, comprise the polymer materials feed is provided, by being enough to keep material in crushing process, to make polymer materials produce chemically changed, and discharge the particle that obtains for using solid state shear to pulverize under the solid-state cooling conditions to apply mechanical energy to polymer materials.The product of Khait can be processed as thermoplastic material.Khait does not openly contain the waste liquid of polymkeric substance, does not indicate how to handle the waste liquid that comprises the plain boiled water that for example comprises emulsion or dispersed polymeres yet.
The inventor is devoted to solve and utilizes the liquid waste of polymeric economically, and plain boiled water polymkeric substance for example prepares the problem of the product of useful shapable material or shaping.
Summary of the invention
According to the present invention, the method for preparing shapable matrix material comprises: by forming chip slurry (crumb slurry) with random order or following step side by side: the particle diameter that (i) increases the waterborne compositions that comprises the plain boiled water refuse that is obtained by one or more thermoplastic emulsions or dispersed polymeres, for example the weight average particle diameter that they reach polymkeric substance by condensing is 1 μ m or bigger, the composition that (ii) will comprise the plain boiled water refuse that is obtained by one or more thermoplastic emulsions or dispersed polymeres (being waste of polymeric) combines with the preferred sulfur product of one or more waste thermoset materials, (iii) randomly, the chip de-watering of slurries is formed crumb mixture, wherein dehydration occur in (i) or (ii) after; And preferably processing forms shapable matrix material or formed article as the chip slurry or the mixture of thermoplastic material in degassing extruder (devolatilizing extruder).Waste of polymeric comprises one or more thermoplastic emulsions or dispersed polymeres.Preferably, for the ease of condensing, the plain boiled water refuse comprises 30 weight % or more, or 50 weight % or more one or more metastable emulsion or dispersed polymeres, based on waste of polymeric solid gross weight.
In one embodiment, the plain boiled water refuse can further comprise the waterborne compositions of the defective thermoplasticity waste of polymeric that one or more can not use or sell.The polymer solids content of the defective polymer composition that is fit to is 20 weight % or still less, and preferred 12 weight % or still less perhaps can be diluted to this polymer solids content.The plain boiled water waste of polymeric can comprise the most nearly defective waste of polymeric of 99 weight %, based on total waste of polymeric solid weight.
In preferred implementation of the present invention, comprise that the weight average particle diameter that condenses or flocculate waste of polymeric in the processed composition of the waterborne compositions of plain boiled water waste of polymeric is increased to 20 μ m or bigger.
The screen cloth particle diameter of waste thermoset material should be 5000 μ m or littler, preferred 2500 μ m or littler, or more preferably 600 μ m or littler.The lower limit of waste thermoset material without limits.But in fact it is 50 μ m or bigger.
Waste thermoset material preferably includes vulcanization of rubber product, for example tire sealant (GTR).Preferably, the composition that comprises the plain boiled water refuse comprises vinylformic acid or vinyl polymer.
In embodiments of the present invention, this method comprises that forming solids content with random order or following step simultaneously is 40 weight % or chip slurry still less: the waterborne compositions that (i) will comprise the plain boiled water refuse that is obtained by one or more thermoplastic emulsions or dispersed polymeres condenses and the composition that (ii) will comprise the plain boiled water refuse that is obtained by one or more thermoplastic emulsions or dispersed polymeres and one or more screen cloth particle diameters are that 600 μ m or bigger waste thermoset material combine; And (iii) with the wet-milling of chip slurry, screen cloth particle diameter to the 600 μ m of reduction chip slurry or littler; (iv) randomly, for example by filtering de-watering of slurries with wet-milling; (v) choose further the slurry of the wet-milling of cleaning or drying or cleaning and drying and dehydrating wantonly; And (v) process chip slurry, form shapable matrix material for example bead or powder as the wet-milling of thermoplastic material, or formed article.
According to the present invention, the method for wet-milling can be selected from solid state shear and pulverize (S 3P), mill and other known wet milling process.
According to the present invention, the thermoplastic material working method can be selected from known method, only is subject to the flowability of chip under the hot plastic processing method condition.This method can for example comprise to be extruded, and granulation is extruded, calendering, injection moulding, compression moulding, rotational molding, and combination.In one embodiment, for example granular extrudate is compression moulding.
But this method can form formed composite material and goods, but described formed composite material and goods comprise 10 to 90 weight % waste thermoset materials based on waste thermoset material and waste of polymeric gross weight, preferred 30 weight % or more, or the waste of polymeric of 50 weight % or more and surplus.
According to the present invention, shapable matrix material can comprise it substantially all being waste materials, but and is the shaping compound of segmentation or the form of passing through the goods of thermoplasticity processing and preparing.Therefore, but can comprise for example bead, powder, particle, sheet material or film, and the molded article of other thermosetting by the formed composite material of thermoplasticity processing and preparing.
In optional embodiment, shapable matrix material can further comprise the novel thermoplastic polymkeric substance of interpolation.The thermoplasticity novel polymer can be before processing be as the chip slurry of thermoplastic material or crumb mixture or in any moment add.
In an embodiment of the invention, shapable matrix material is made up of the not crosslinked composition of work in-process substantially, for example by thermoplastic polymer that derives from the plain boiled water refuse to small part and 10 to 90 weight % waste thermoset materials, based on the gross weight of waste thermoset material and thermoplastic polymer.
Unless specialize, any term that comprises bracket refers to alternatively, if do not have bracket to exist then be whole term scope and the term scope that does not have their (contents of promptly getting rid of bracket), and the combination of various selections.Therefore, term " (methyl) acrylic acid series " refers to acrylic acid series arbitrarily, metha crylic and composition thereof.
All scopes all be comprise and be combinative.For example, weight average particle diameter is 1 μ m or bigger, or 10 μ m or bigger, or is up to 5000 μ m, or be up to 1000 μ m, or preferred 20 μ m or bigger, or preferably be up to 600 μ m and comprise that scope is 1 to 10 μ m, 1 to 20 μ m, 1 to 600 μ m, 1 to 1000 μ m, 1 to 5000 μ m, 10 to 20 μ m, 10 to 600 μ m, 10 to 1000 μ m, 10 to 5000 μ m, 20 to 600 μ m, 20 to 1000 μ m, 20 to 5000 μ m, 600 to 1000 μ m, 600 to 5000 μ m and 1000 to 5000 μ m.
Herein, term " acrylic acid series " refers to mainly by acrylate, methacrylic ester, acrylic or methacrylic acid or (methyl) propenal monomer, the material that polymkeric substance or resin make.
Herein, phrase " water-based " comprises water and mixture, but described mixture is included in 50 weight % or more water in the mixture of water and water-miscible solvent.
Herein, unless specialize, term " second-order transition temperature " or " Tg " refer to by dsc (TA Instrument model Q-1000) at-90 ℃ to the 150 ℃ second-order transition temperatures with the material of 20 ℃ of/minute rate scannings mensuration.Tg is a point of inflexion on a curve.
Herein, unless specialize, term " second-order transition temperature of calculating " or " Tg of calculating " refer to by as Fox at American Physical Society's communique (Bulletin of the American Physical Society), 1, the second-order transition temperature of the material that Fox's equation (Fox Equation) of describing in 3, the 123 pages (1956) is measured.
Herein, unless specialize term " polymer " " comprise homopolymer individually, multipolymer, terpolymer, segmented copolymer, fragment multipolymer, graft copolymer, and mixture or combination arbitrarily.
Herein, term " screen cloth particle diameter " refers to that all material all passes through the particle diameter of the mesh screen of given particle diameter.For example, be considered to have the screen cloth particle diameter of 203 micron-scales by the GTR of 203 micron-scales sieves (60 order).For given material, the screen cloth particle diameter will be greater than weight average particle diameter.
Herein, term " substantially all being the waste materials that reclaims " refers to comprise any materials of at least 97 weight % waste of polymeric and waste thermoset material.Its gets rid of filler and any non-polymer material that can physical sepn goes out from material, for example metal wire.Therefore, comprising the waste of polymeric of for example 5 to 10% clay flocculating agent and remainder or the material of waste thermoset material can be the material of " substantially all being the waste materials that reclaims ".
Herein, unless specialize, term " weight average particle diameter " refers to Malvern Mastersizer 2000 TMParticle size analyzer (the weight average particle diameter of the material that the Ma Erwen instrument company (Malvern Instruments Ltd., Malvern, Worcestershire, UK)) that is positioned at the Britain Worcestershire measures with light scattering technique.Material can comprise the polymkeric substance and the aggregate thereof of agglomerative or flocculation.
Herein, term " plain boiled water " refers to the refuse by aqueous polymer emulsion or dispersion liquid processing generation, comprises effluent and the waste material polymer emulsion or the dispersion liquid of washing processing equipment.
But the invention provides formed composite material and molded article prepared therefrom by polymkeric substance that reclaims and elastomeric material preparation.The inventor finds that processing the plain boiled water that produces by waste of polymeric can reclaim fully, consequently can dewater as long as the particle diameter of solid or thermoplastic emulsion or dispersion waste of polymeric is enough big.In addition, the inventor finds that also isolated various waste of polymeric solids can form compatible mixture with various waste thermoset materials effectively in thermoplasticity processing from plain boiled water.Can use some Polymer wastes streams simultaneously.In addition, do not need compatilizer to prepare useful shapable matrix material, need between waste thermoset material and waste of polymeric, chemical reaction not take place yet.Not adding compatilizer or linking agent provides extra advantage, and material according to the invention can be the thermoplastic material of reprocessing and can reclaim once more at last.In addition, the invention provides and comprise at high proportion 50 weight % for example or higher waste thermoset material especially as the material of sulfur waste products such as GTR.
The mechanical property of the product that the present invention obtains (comprises elongation, intensity and modulus) suitable with the performance of composites for preparing in the same manner by identical novel polymer, particularly when the polymkeric substance that obtains by plain boiled water be that useless acrylic acid series or vinyl are for example during styrene polymer.
Be used for the defective waste of polymeric of thermoplasticity that the suitable composition that comprises plain boiled water of the present invention can comprise the water-based of plain boiled water thermoplasticity waste of polymeric and dilution, its thermoplastic polymer emulsion or dispersion liquid by any one or multiple water-based obtains, for example be selected from acrylic acid series, vinyl is vinylbenzene for example, styrene-propene acid system and alkyl vinyl ether, vinyl ester, synthetic latex, isoprene for example, divinyl such as styrene butadiene, styrene-acrylonitrile-butadiene, and nitrile rubber, natural rubber latex, and composition thereof and combination of polymers.Acrylic acid series and vinyl polymer are preferred.
One preferred embodiment in, for the ease of processing to increase waste of polymeric particle diameter and/or solid, the waterborne compositions that comprises plain boiled water comprises the plain boiled water that at least some are obtained by metastable polymer emulsion or dispersion liquid, for example adopt those to contain dispersible monomer residuum and be 5 weight % or polymerisate still less based on the weight of polymer solids, preferred 3 weight % or still less, or the tensio-active agent that comprises is for based on 2 weight % of the weight of polymer solids or still less, preferred 1 weight % or still less.Preferred metastable emulsion is acrylic acid series or vinyl polymer emulsion.Herein, term " dispersible monomer " has acid when referring to polymerization, acid salt, hydroxyl, any polymerisable monomer of amine or amine salt functional group.The quantity of metastable polymkeric substance can be 30 weight % or more in the plain boiled water waste of polymeric, or 50 weight % or more, based on total polymer solid in the waste of polymeric composition.
The composition that comprises the plain boiled water waste of polymeric can be selected according to its second-order transition temperature (Tg), makes shapable mixture or composite article be used for special purpose.For example, the polymkeric substance with 20 ℃ or higher Tg is generally used for the floor, and ceramic tile and molding are used, and is used to film and is suitable for the application of relatively hard materials, goods and film; And the polymkeric substance with the Tg that is lower than 20 ℃ is used for sealing agent and filler, asphalt applications and be suitable for rubber-like or the application of toughness material, goods or film.
Mix for the best that obtains waste of polymeric and waste thermoset material, particle diameter separately should be approaching as much as possible mutually.Therefore, the polymer beads that is obtained by waste of polymeric is big as far as possible, and the waste thermoset material particle should be as far as possible little.
The inventor finds to comprise that the condensing of waterborne compositions of plain boiled water waste of polymeric is to make waste of polymeric obtain the efficient manner of appropriate particle size and solids content.Increase waste of polymeric particle diameter to the alternate manner of desirable weight average particle diameter and solids content comprises flocculation, if the quantity of flocculation agent and mechanical property and the toughness that type does not influence final product, lyophilize, and combination.
Useful condensing agent comprises any known condensing agent, for example is selected from salt arbitrarily, and for example sodium-chlor or iron(ic) chloride (ferric iron) are FeCl 3, ferric sulfate (ferrous iron) is Fe 2(SO 4) 3, alum is Al 2(SO 4) 3, sal epsom, or preferred FeCl 3Acid, for example formic acid or sulfuric acid of carboxylic acid for example is with the pH to 4.5 that reduces the plain boiled water polymkeric substance or lower, preferred 4.0 or lower; Chemical coagulation agent and composition thereof.Acid is preferred, can reduce the demand of repeated washing polymer product.Other chemical coagulation agent can comprise aluminum oxide, aluminum chlorohydrate (aluminium chlorohydrate), calcium oxide, polyacrylamide, sodium aluminate and water glass etc.; Can comprise chitosan (chitosan) with the natural product condensing agent, the Moringa oilseeds, papoid, nux vomica seed (strychnos seeds), and fish glue are except that other.
The flocculation agent that is fit to comprises clay, and for example kaolin uses with conventional quantity.
The consumption of condensing agent or flocculation agent can be 0.25 to 10 weight %, and preferred 1 to 7 weight % is based on the gross weight of plain boiled water polymer solids.
For with combine (combine) of waste thermoset material, the waste of polymeric particulate weight average particle diameter that is fit to can be preferably as much as possible near the screen cloth particle diameter of waste thermoset material.But the polymkeric substance weight average particle diameter that is fit to is 1 μ m or bigger, or 10 μ m or bigger, or is up to 5000 μ m, or is up to 1000 μ m, or preferred 20 μ m or bigger, or preferably is up to 600 μ m.If the polymkeric substance weight average particle diameter is lower than 1 μ m, undesirable waste of polymeric loss then can take place in dehydration or cleaning process.
The waterborne compositions that comprises the plain boiled water polymkeric substance is fit to condense or flocculate, and is 2.0 weight % or more so that before dehydration its solids content is increased to the total polymer solid, preferred 4 weight % or more, or 5 weight % or more, and be up to 40 weight %.
In preferred embodiment, the ratio of the weight average particle diameter of the waste of polymeric of agglomerative or flocculation and the weight average particle diameter of waste thermoset material is 1: 20 to 5: 1, or preferred 1: 10 or more.
In another embodiment, waste of polymeric composition (those of solids content that promptly have increase) can be directly used in the preparation compound resin, need not dehydration.Dehydration and redispersion make polymkeric substance conveniently store and transportation.
The waste thermoset material that is fit to can comprise the Polymer wastes that any particulate state is crosslinked, for example by vulcanization of rubber product for example GTR or sole rubber; Solidified urethane (urethane) is polyurethane foam for example; Hard end plastics (ground hard plastics) are for example from urethane, polycarbonate, Resins, epoxy, aminoplast(ic) resin, those that resol such as P-F and cross-linked polyolefin (PEX) obtain.Waste thermoset material can further comprise filler, for example carbon black, silicon-dioxide, silicate and aluminum oxide.
The screen cloth particle diameter of the waste thermoset material that is suitable for is 50 to 5000 μ m, for example 177 μ m or bigger, or 180 μ m or bigger.Waste thermoset material can be, shred for example, and rubber is coccoid, rubber pencil, or chip or Powdered.
Making waste of polymeric and waste thermoset material combination by milling or mixing, form the chip slurry, perhaps, is crumb mixture if waste of polymeric dewatered before combination.
The combination of preparation chip slurry can be chosen wantonly and comprise wet-milling.Dehydration after the wet-milling, and if desired, the dry processing chip.
In embodiments of the present invention, wherein the screen cloth particle diameter of waste thermoset material is 600 μ m or bigger, with bonded waste thermoset material and waste of polymeric wet-milling, to reduce the weight average particle diameter of waste thermoset material in the mixture.
The wet-grinding technology and relative device that is fit to comprises that the mixture of pulverizing waste thermoset material and waste of polymeric as slurry, reduces the waste thermoset material particle grain size thus, contacts waste of polymeric simultaneously closely.For example, the solid state shear that can apply to the slurry mix of waste of polymeric and waste thermoset material by wet-milling is pulverized (S 3P).Wet-milling can be implemented in pan mill or twin screw extruder, perhaps can comprise solid state shear pulverizing (S 3P).Other technology that is fit to includes but not limited to pulverize, for example at the rotation masher, and disc refiner, stoning machine is in the plastic crusher; And other disintegrating process, for example the Berstorff pulverizer is extruded pulverizing, and solid state shear is extruded and Brubender extrudes.Solid state shear is extruded (SSSE) and is heated under molten state or under envrionment conditions, can be used for the water paste mixture.Preferably, wet-milling comprises S 3P, it is defined as to solid particulate and applies the intensive shear-stress with the non-fusion pulverizing of the waste thermoset material under the solid-state waste of polymeric existence, and implements to material under envrionment temperature or cooling conditions.
Wet-milling or S 3P can not cause the chemical reaction of any non-thermosettable material and waste of polymeric.But the chip that forms in wet milling process of the present invention can demonstrate the tensile failure and the low-temperature flexibility of improvement than waste thermoset material or the independent polymkeric substance that is obtained by plain boiled water.
Method of the present invention can further comprise the chip de-watering of slurries and randomly, the chip that cleaning obtains is to remove impurity in the thermoplasticity first being processed.The dehydration of chip slurry for example comprise solid (little) filtered or centrifugation to remove unnecessary water.
This method can also comprise the crumb mixture drying that dehydration is obtained.Randomly, in some embodiments, the chipped material of dehydration can be by strand, press dry dry or drying is carried out in lyophilize.Also can use conventional drying means, comprise and for example use baking box or drying machine for example Vacuumdrier, blast dryer, rotary dryer or hand dryer.
Method of the present invention further comprises carries out thermoplasticity processing with crumb mixture or chip slurry, and can further reduce moisture content in this course of processing.Thermoplasticity processing can comprise the kneading chipped material, randomly heating and randomly remove volatile material.Kneading can use two roller pan mills (two-roll mill) to realize, or by for example extruded material in degassing extruder, or be sent to injection moulding machine in some cases.Thermoplasticity processing can directly make composite formed one-tenth goods, and for example by extruding, perhaps it can form shapable matrix material for example bead, particle or powder.Similarly, two roller pan mills can be united use with compression moulding, and making material transition is moulded product.Thermoplasticity processing also can comprise heating or calendering, pressing mold, rotational molding or the injection moulding of not heating.Preferably, thermoplasticity is processed in the twin screw extruder that is included in reverse rotation and is mediated.
In embodiments of the present invention, can use and extrude or similar melt-processed technology, to form shapable matrix material, particle for example, powder or bead, they can form molded article or subsequently as filler or sealing agent.
But formed composite material of the present invention can be processed into the material of segmentation or the goods of arbitrary shape by thermoplasticity, for example sheet material and film, or as the material of molding or shaping.Film prepared in accordance with the present invention can be used for being formed for the multi-layer product and the laminated product of many purposes.
In one embodiment, but formed composite material of the present invention comprises it substantially all being Recycled materials.Alternatively, can the thermoplasticity first being processed or in add one or more novel thermoplastic polymkeric substance reach total composite composition 50 weight % most.
Shapable matrix material can be as required or the requirement of the end-use of mixture chip comprise various additives in addition, one or more vulcanizing agents for example, thermosetting resin or polymkeric substance, oxidation inhibitor, UV stablizer, fire retardant, tinting material, filler is with for example powder, fiber, the form of rectangular or fragment; Strongthener, for example non-woven fabrics, or scrim, pigment, thermosetting resin or polymkeric substance, heat-setting (curable) resin or polymkeric substance, and processing aid, for example releasing agent and low quantity of surfactant.Additive can the thermoplasticity first being processed or among add.
The useful the finished product of shapable matrix material comprise, but do not sink into, trolley part, tire for example, snubber, packing ring, fan belt, wiper blade, liner, damping device, underbody coating, thermal insulation barriers and decoration (trim); Building products is roof film for example, roof tiles or roof felt, geomembrane, insulcrete, deadener, rain visor, modified epdm roof film and pitch strongthener; The bituminous seal agent is used for the seam sealer and the bituminous concrete highway surfacing material of pitch and cement; Concrete modifying material; The modified chloroprene rubber goods; Ceramic tile or ceramic tile backing; Carpet backing; Sound-proof material; The sound absorption bed course; Floor cushion coat and seat; Industrial products for example are used for the liner of made ground; Sporting goods is artificial turf and runway for example; The playground surface; Mat and liner; Ball core and consuming product are floor tile or floor for example; Sole; Liner; Cover; And layered product, gardening jar for example, the family expenses annex of molding and the ornament of molding; With other purposes, for example friction lining, timber floor backing, cable insulation material, gardening flexible pipe, tool kit handle and furniture leg pad.
In one embodiment, but hotmelt can comprise and account for the present invention's formed composite material 40 weight % or more thermoplasticity waste of polymeric solid.
In another embodiment, but formed composite material can be formed for the film of laminated product.Laminated product can comprise as one deck or two-layer or multiwalled matrix material, for example strengthens the laying of EPDM roof film, rubber-like supporting layer in the toughness sheet material or laying and the adhesive tape with binder layer.The layer of sloughing that can have optional binder layer and protection binder layer as any laminate product of roller storage.
Embodiment
In the following example, the tensile strength of the sheet material of assessment preparation, elongation at break (%E) and tear strength, according to following testing method:
Processing and implementation example 1: will contain 1% solid plain boiled water and be processed into wet cake.
With 3 processing unit (plant) Bristol, PA (embodiment 1), Knoxville, TN (embodiment 2) and Charlotte, NC (embodiment 3) will make sample in 90BA/9MMA/1MAA (reactant weight) to the whitewater emulsion shaped polymer that the mixture of 40BA/39MMA/1MAA ratio obtains by butyl acrylate/methyl methacrylate/methacrylic acid (BA/MMA/MAA) polymkeric substance.
Total quantity by polymer solids in the solids content estimation plain boiled water of measuring plain boiled water and calculate based on the cubic capacity of settling pond (retention pit).Under moderate agitation, add FeCl to the plain boiled water dispersion liquid 3Solution (40%).Total FeCl with respect to the polymer solids meter 3Be 6 weight %.Agglomerative latex polymer (～5% solid) sinks down into the bottom, pond and is pumped to centrifugal dehumidifier, becomes wet pie with concentrated polymer.Measure the solid of wet cake by gravimetry, and be shown in down in the tabulation 1.
Table 1: agglomerative plain boiled water polymer solids
Embodiment 1 The % solid
??1 ??41.2
??2 ??42.6
??3 ??62.4
Embodiment 2: form tire sealant (GTR) crumb mixture
Be 35 polymkeric substance/65 rubber (w/w) mixture of preparation 250g, the wet cake of the Sample A (41% solid) of 213g be scattered in the water of 875g, and stir the GTR 150 μ m chips that add 162.5g.With polymkeric substance/rubber composite slurry (20% solid polymkeric substance and rubber) thorough mixing 15 minutes, then by 10 microns filter bags with solid filtering.Unnecessary hydraulic pressure is squeezed out to come and the mixture solid drying 12 hours of will wetting under 60 ℃ in vacuum oven.
Embodiment 3: crumb mixture thermoplasticity is processed into sheet material
In two roller pan mills, processed 250g dry mixture solid (＜5 weight % moisture content) 2 minutes down and pass through safe water press (Reliable Hydraulic Press) (safe rubber and plastics machinery company, N.J. north uncle's root (Reliable Rubber ﹠amp for 195 ℃; Plastics Machinery Company, NorthBergen, New Jersey)) under 195 ℃, 0.102 (40 mil thick) is being housed, 25.4cm compression moulding is 5 minutes altogether between the steel plate of * 25.4cm (10 inches * 10 inches) framework, with following pressure: 1 minute 3.45E7 pascal (5000psi); 1 minute 6.89E7 pascal (10000psi) and 3 minutes 1.65E8 pascals (24000psi), afterwards in the chilling press of recirculated water is housed at 1.65E8 pascal (24000psi)) at room temperature cooled off 5 minutes under the pressure.
Embodiment 4: the testing method of mechanical property and tear strength
The mixture sample that embodiment 3 is obtained be cut into 7.62cm L * 1.27cm W * 0.102cm thick (3 " * 1/2 " * 40 mils) molding sheet material of rectangular strip.(Tinius Olsen Inc., Horsham PA) go up measurement tensile strength and elongation at Tinius Olsen H10KS tension testing machine according to ASTM D-2370 (ASTM Volume06.01, in February, 2008) agreement.Pinblock speed be 2.54cm (1.0 inches)/minute and gauge length be 2.54cm (1.0 inches).Test descends and controls relative humidity to carry out for 50% time for 23 ℃ at controlled temperature.By the elongation at break of this each sample of thermometrically, maximum stress (tensile strength) and energy-to-break.
Test the airborne measurements tear strength according to ASTM D624 (ASTM Volume in July, 09.01,2008) at Tinius Olsen H10KS.With constant 50.8cm (20 ")/minute the horizontal speed of pinblock apply to specimen (the Type C punch die of describing in by ASTM D624 is sheared) (ASTM Volume in July, 09.01,2008) and tear tension force and tear fully until sample.
In comparative example 1A and 2A, polymkeric substance is to condense and the blended novel polymer with waste thermoset material, by injecting 875g water to the mixing vessel that mechanical stirrer is housed, adds 9.4g FeCl by 40 weight % aqueous solutions in water 3Stirring down, adding 125g screen cloth particle diameter is ground rubber for tire (the Edge Rubber of 180 μ m (80 order), Chambersburg, Pennsylvania) be dispersed in aqueous phase until all rubber grains and form slurry, add 250g polymer latex (50% solid w/w) and stirred 15 minutes to slurry then.Kept agglomerative polymkeric substance/rubber slurry balanced 12 hours and obtained polymkeric substance/rubber scraps mixture with the filtration of 10 μ m filter bags.Clean solid three times by the filter bag water.Squeeze out unnecessary water and in vacuum oven 60 ℃ of following dry wet solids 12 hours, obtain the exsiccant crumb mixture.
Test result is shown in down in the tabulation 2.
Table 2: mechanical property and toughness
Embodiment Tg (℃) (peak value) Maximum pull (psi) Maximum elongation rate (%) Tear strength
??1 (14.9/46.2 wide) ??619 ??217 ??149
??2 -46.7/36.9 (wide) ??658 ??110 ??139
??3 (34.4 wide) ??692 ??377 ??191
??1A 1Comparative Examples 20 (narrow) ??681 ??377 ??172
??2A 2Comparative Examples -6 (narrow) ??164 ??448 ??53
1. comparative example 1A 47 BA/52 MMA/1 MAA, Tg is 20 ℃.
2. comparative example 2A 70 BA/29 MMA/1 MAA, Tg is-6 ℃.
The embodiment of the invention 1,2 and 3 mechanical property can with comparing by the novel polymer latex preparation among comparative example 1A and the 2A.The second-order transition temperature of polymkeric substance (Tg)＞0 ℃ among the comparative example 1A.In the plain boiled water polymeric blends, tensile property keeps well surprisingly, even they contain flexible polymer.For example used among the comparative example 2A in softer novel polymer, along with the increase tensile strength of elongation reduces.

Claims (10)

1. method for preparing shapable mixture, described method comprises:
By with random order or side by side following steps form the chip slurry: (i) increase the particle diameter of the waterborne compositions that comprises the plain boiled water refuse that obtains by one or more thermoplastic emulsions or dispersed polymeres and will comprise that (ii) the composition of the plain boiled water refuse that is obtained by one or more thermoplastic emulsions or dispersed polymeres combines with one or more waste thermoset materials;
Randomly, the chip de-watering of slurries is formed crumb mixture, wherein dehydration occurs in (i) afterwards or (ii); And,
Processing forms shapable matrix material as the chip slurry or the mixture of thermoplastic material.
2. the method as requiring in the claim 1, wherein the plain boiled water refuse comprises 30 weight % or more one or more metastable emulsion or dispersed polymeres, based on waste of polymeric solid gross weight.
3. as the method for requirement in the claim 1, wherein the plain boiled water refuse comprises the most nearly defective waste of polymeric of 99 weight %, based on total waste of polymeric solid weight.
4. the method that requires in the claim 1, wherein the plain boiled water refuse comprises one or more acrylic acid seriess or vinyl polymer.
5. the method that requires in the claim 1 wherein increases particle diameter and comprises and condense or flocculate.
6. the method that requires in the claim 5, wherein increasing particle diameter, to cause the polymer composition weight average particle diameter be 1 μ m or bigger.
7. the method that requires in the claim 6, wherein the screen cloth particle diameter of waste thermoset material is 600 μ m or bigger, this method further comprises:
Before any dehydration with the wet-milling of chip slurry, with screen cloth particle diameter to the 600 μ m that reduces the chip slurry solids or littler,
Randomly, the de-watering of slurries with wet-milling forms crumb mixture; With
Randomly, the slurry of the wet-milling of cleaning and/or drying and dehydrating,
Wherein, the chip slurry had 40 weight % or lower solids content before wet-milling.
8. the method that requires in the claim 7, wherein wet milling process is selected from solid state shear and pulverizes (S 3P) and mill.
9. the method that requires in the claim 1 is wherein processed and is comprised as the chip slurry of thermoplastic material or mixture and to extrude that granulation is extruded, calendering, injection moulding, compression moulding, rotational molding, and combination.
10. but shaping compound that work in-process is not crosslinked, described mixture is basically by forming from the thermoplastic polymer and 10 to the 90 weight % waste thermoset materials of plain boiled water refuse to small part, based on the gross weight of waste thermoset material and thermoplastic polymer.
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